Core Cross-Linked Multiarm Star Polymers with Aggregation-Induced Emission and Temperature Responsive Fluorescence Characteristics

Handle URI:
http://hdl.handle.net/10754/624999
Title:
Core Cross-Linked Multiarm Star Polymers with Aggregation-Induced Emission and Temperature Responsive Fluorescence Characteristics
Authors:
Zhang, Zhen; Bilalis, Panagiotis ( 0000-0002-5809-9643 ) ; Zhang, Hefeng; Gnanou, Yves ( 0000-0001-6253-7856 ) ; Hadjichristidis, Nikolaos ( 0000-0003-1442-1714 )
Abstract:
Aggregation-induced emission (AIE) active core cross-linked multiarm star polymers, carrying polystyrene (PS), polyethylene (PE), or polyethylene-b-polycaprolactone (PE-b-PCL) arms, have been synthesized through an “arm-first” strategy, by atom transfer radical copolymerization (ATRP) of a double styrene-functionalized tetraphenylethene (TPE-2St) used as a cross-linker with linear arm precursors possessing terminal ATRP initiating moieties. Polyethylene macroinitiator (PE–Br) was prepared via the polyhomologation of dimethylsulfoxonium methylide with triethylborane followed by oxidation/hydrolysis and esterification of the produced PE–OH with 2-bromoisobutyryl bromide; polyethylene-block-poly(ε-caprolactone) diblock macroinitiator was derived by combining polyhomologation with ring-opening polymerization (ROP). All synthesized star polymers showed AIE-behavior either in solution or in bulk. At high concentration in good solvents (e.g., THF, or toluene) they exhibited low photoluminescence (PL) intensity due to the inner filter effect. In sharp contrast to the small molecule TPE-2St, the star polymers were highly emissive in dilute THF solutions. This can be attributed to the cross-linked structure of poly(TPE-2St) core which restricts the intramolecular rotation and thus induces emission. In addition, the PL intensity of PE star polymers in THF(solvent)/n-hexane(nonsolvent) mixtures, due to their nearly spherical shape, increased when the temperature decreased from 55 to 5 °C with a linear response in the range 40–5 °C.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division; Polymer Synthesis Laboratory
Citation:
Zhang Z, Bilalis P, Zhang H, Gnanou Y, Hadjichristidis N (2017) Core Cross-Linked Multiarm Star Polymers with Aggregation-Induced Emission and Temperature Responsive Fluorescence Characteristics. Macromolecules 50: 4217–4226. Available: http://dx.doi.org/10.1021/acs.macromol.7b00506.
Publisher:
American Chemical Society (ACS)
Journal:
Macromolecules
Issue Date:
19-May-2017
DOI:
10.1021/acs.macromol.7b00506
Type:
Article
ISSN:
0024-9297; 1520-5835
Sponsors:
Research reported in this publication was supported by King Abdullah University of Science and Technology (KAUST).
Additional Links:
http://pubs.acs.org/doi/full/10.1021/acs.macromol.7b00506
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorZhang, Zhenen
dc.contributor.authorBilalis, Panagiotisen
dc.contributor.authorZhang, Hefengen
dc.contributor.authorGnanou, Yvesen
dc.contributor.authorHadjichristidis, Nikolaosen
dc.date.accessioned2017-06-14T12:17:32Z-
dc.date.available2017-06-14T12:17:32Z-
dc.date.issued2017-05-19en
dc.identifier.citationZhang Z, Bilalis P, Zhang H, Gnanou Y, Hadjichristidis N (2017) Core Cross-Linked Multiarm Star Polymers with Aggregation-Induced Emission and Temperature Responsive Fluorescence Characteristics. Macromolecules 50: 4217–4226. Available: http://dx.doi.org/10.1021/acs.macromol.7b00506.en
dc.identifier.issn0024-9297en
dc.identifier.issn1520-5835en
dc.identifier.doi10.1021/acs.macromol.7b00506en
dc.identifier.urihttp://hdl.handle.net/10754/624999-
dc.description.abstractAggregation-induced emission (AIE) active core cross-linked multiarm star polymers, carrying polystyrene (PS), polyethylene (PE), or polyethylene-b-polycaprolactone (PE-b-PCL) arms, have been synthesized through an “arm-first” strategy, by atom transfer radical copolymerization (ATRP) of a double styrene-functionalized tetraphenylethene (TPE-2St) used as a cross-linker with linear arm precursors possessing terminal ATRP initiating moieties. Polyethylene macroinitiator (PE–Br) was prepared via the polyhomologation of dimethylsulfoxonium methylide with triethylborane followed by oxidation/hydrolysis and esterification of the produced PE–OH with 2-bromoisobutyryl bromide; polyethylene-block-poly(ε-caprolactone) diblock macroinitiator was derived by combining polyhomologation with ring-opening polymerization (ROP). All synthesized star polymers showed AIE-behavior either in solution or in bulk. At high concentration in good solvents (e.g., THF, or toluene) they exhibited low photoluminescence (PL) intensity due to the inner filter effect. In sharp contrast to the small molecule TPE-2St, the star polymers were highly emissive in dilute THF solutions. This can be attributed to the cross-linked structure of poly(TPE-2St) core which restricts the intramolecular rotation and thus induces emission. In addition, the PL intensity of PE star polymers in THF(solvent)/n-hexane(nonsolvent) mixtures, due to their nearly spherical shape, increased when the temperature decreased from 55 to 5 °C with a linear response in the range 40–5 °C.en
dc.description.sponsorshipResearch reported in this publication was supported by King Abdullah University of Science and Technology (KAUST).en
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://pubs.acs.org/doi/full/10.1021/acs.macromol.7b00506en
dc.titleCore Cross-Linked Multiarm Star Polymers with Aggregation-Induced Emission and Temperature Responsive Fluorescence Characteristicsen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentPolymer Synthesis Laboratoryen
dc.identifier.journalMacromoleculesen
kaust.authorZhang, Zhenen
kaust.authorBilalis, Panagiotisen
kaust.authorZhang, Hefengen
kaust.authorGnanou, Yvesen
kaust.authorHadjichristidis, Nikolaosen
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